KR101739259B1 - New pyrrole monomer and manufacturing method thereof, polymer or compound from new pyrrole monomer and manufacturing method thereof - Google Patents
New pyrrole monomer and manufacturing method thereof, polymer or compound from new pyrrole monomer and manufacturing method thereof Download PDFInfo
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- KR101739259B1 KR101739259B1 KR1020150056775A KR20150056775A KR101739259B1 KR 101739259 B1 KR101739259 B1 KR 101739259B1 KR 1020150056775 A KR1020150056775 A KR 1020150056775A KR 20150056775 A KR20150056775 A KR 20150056775A KR 101739259 B1 KR101739259 B1 KR 101739259B1
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- SKYYNHPVQWZDLS-UHFFFAOYSA-N C1Oc2c[s]c(-c(c3n[s]nc33)c4nsnc4c3-c3c4OCCOc4c[s]3)c2OC1 Chemical compound C1Oc2c[s]c(-c(c3n[s]nc33)c4nsnc4c3-c3c4OCCOc4c[s]3)c2OC1 SKYYNHPVQWZDLS-UHFFFAOYSA-N 0.000 description 1
- BOBBMLSEPMCXDT-UHFFFAOYSA-N Cc(c(C)nc1c(c2n[s]nc22)-c3c4OCCOc4c[s]3)nc1c2-c1c2OCCOc2c[s]1 Chemical compound Cc(c(C)nc1c(c2n[s]nc22)-c3c4OCCOc4c[s]3)nc1c2-c1c2OCCOc2c[s]1 BOBBMLSEPMCXDT-UHFFFAOYSA-N 0.000 description 1
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- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
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- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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Abstract
The present invention relates to a novel pyrrole monomer and a process for producing the same, a polymer or compound synthesized from a pyrrole monomer, and a process for producing the same, and its object is to introduce an alkyl chain, And to provide a novel pyrrole monomer capable of producing a conductive polymer or compound having high conductivity, a method for preparing the same, a polymer synthesized using the same, a method for producing the same, and a compound and a method for producing the same.
The novel pyrrole monomers of the present invention can produce various polymers and copolymers by allowing the polypyrrole derivatives to be insoluble in organic solvents by introducing an alkyl chain to have high solubility, Lt; / RTI >
Description
The present invention relates to a novel pyrrole monomer and a process for producing the same, a polymer or compound synthesized from the pyrrole monomer and a process for producing the same, and more particularly to a process for synthesizing a novel pyrrole monomer having a pi- To a novel conductive polymer having high conductivity and a compound which is synthesized with various materials.
Organic single molecules or polymers having a conjugated system, that is, a pi-conjugated structure, have been found to have semiconducting properties due to structural characteristics of molecules, and various studies have been conducted as organic semiconductor materials.
The constituent unit molecules of the organic semiconductor can be classified into a small molecule or a polymer (macromolecule) type according to the length of the molecule, and examples of the organic monomolecular molecule include oxoquinoline aluminum (III) (III): AlQ3), pentacene, and rubrene are known. Examples of organic polymers include poly (p-phenylenevinylene) (PPV), polythiophene polythiophene (PTh) and derivatives thereof are known to have excellent electrical and photoreactivity. Light absorption characteristics, light and electroluminescence phenomena, and charge transport characteristics thereof are currently being investigated.
In the case of organic semiconductors in which the organic monomolecules are constituent monomolecules, the carbon atoms constituting the compound include pi-conjugation repeating a single covalent bond and a double covalent bond sharing a pi (2π) ) Structure.
In particular, conjugated monomolecular and polymer systems with a donor-acceptor structure can be applied to transparent conductors, thin-film transistors, organic light-emitting devices (OLEDs: Organic Light Emitting Diodes or organic EL) Various studies have been carried out.
For example, the present inventors have reported a conjugated conducting polymer comprising thiophene and benzobisthiazole (In Tae Kim, et al., Synthetic Metals 156 (2006) 38-41) 2-nonyl-thieno [3,4- d ] thiazole copolymers have been reported (In Tae Kim, et al., Bull. Korean Chem. Soc. , 2511-2513) and also reported the X-ray structure and properties of dithiopyrrole and Pd (II) or Pt (II) complexes (Jun-Gill Kang et al., Bull. (2008), Vol. 29, No.3, 679-681 and Jun-Gill Kang et al., Bull. Korean Chem. Soc. ( 2008), Vol. 29, No. 3, 599-603).
In addition, Chia-Ling Pai et al. Have found that a portion of a molecule that attracts electrons well (3,4-ethylene oxide cyanophene, EDOT) and a moiety that provides good electrons (for example, thiazole, thiadiazole, (Chia-Ling Pai et al., Polymer (2006), 47, 699-708) have been reported.
In recent years, there have been reported examples of applying conjugated oligomers having EDOT (3,4-ethylenedioxythiophene) on both sides to organic light emitting devices as follows (Yixing Yang et al. Applied Physics Letters (2008), 93, 163305).
In general, when an ethylene group is introduced between aromatic rings, the molecular weight is increased during the polymerization of the polymer to decrease the band gap. As a result, the semiconductor and solar cell properties such as the increase of the conductivity and the absorption of the wavelength in the near infrared region are improved, and the applicability of the conductive polymer can be improved.
On the other hand, oligomers are composed of two or more monomeric bonds, and they are used for predicting the properties of oligomers, related derivatives, and polymers having similar structures by measuring physical, chemical, electrical, stereoscopic, and optical properties appearing in their bonding.
Particularly, conjugated oligomers composed of carbon in which single bonds and double bonds are repeated are used in electronic devices such as electrochromic devices, transistors, and sensors.
In general, an oligomer consisting of a donor and an acceptor repeating structure is formed by the hybridization of the high HOMO energy of the donor and the low LUMO energy of the acceptor, The band gap, which is a value indicating a difference, tends to be lowered. Therefore, it has better electrical characteristics and optical properties, which can be more useful for LED and solar cells.
Also, polypyrrole and derivatives thereof (see Handbook of Conducting Polymers (Edited by T. A Skotheim), Marcel Dekker (1986)) well known as a conductive polymer have been studied for antistatic materials, electrode materials and discoloring materials .
However, the polypyrrole polymer materials have the disadvantage that the final material is insoluble in the organic solvent. Therefore, there is a need for a polypyrrole polymer material which can solve this problem.
It is an object of the present invention to solve the above problems and to provide a novel conductive polymer or compound capable of producing a conductive polymer or compound having a high conductivity by introducing an alkyl chain and having a high solubility in an organic solvent and a low band gap, And a manufacturing method thereof.
Another object of the present invention is to provide a polymer having a low degree of steric hindrance and high conductivity using a novel pyrrole monomer and a method for producing the same.
Another object of the present invention is to provide a compound capable of synthesizing a novel pyrrole monomer and having excellent electronic properties and high solubility in an organic solvent, and being applicable to various technical fields, and a method for producing the same.
Disclosure of Invention Technical Problem [8] The present invention for achieving the above object and accomplishing the object of eliminating the conventional drawbacks is achieved by providing a novel pyrrole monomer represented by the following general formula (1).
[Chemical Formula 1]
Wherein R 1 is
The present invention also provides, in another embodiment, a process for the preparation of 4-heptadecyl-5-hexyl-5,6-dihydro- dihydro- 4H -pyrrolo [3,4-d] thiazole;
b) Addition of 1,2-dichloro-5,6-dicyano-hydroquinone to the synthesized 2-heptadecyl-5-hexyl-5,6-dihydro- 4H- pyrrolo [3,4-d] To synthesize 2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole;
c) Preparation of a novel pyrrole monomer represented by the following formula (1a) synthesized by dissolving synthesized 2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole in a solvent and then adding bromine or N-bromosuccinimide ≪ / RTI >
[Formula 1a]
In Formula (1a), R 1 is
In a preferred embodiment, the alkyl group on the amine in step a) may comprise C1-C6 alkyl.
In another embodiment, the present invention is achieved by providing a polymer synthesized from a pyrrole monomer represented by the following formula (2) synthesized using the novel pyrrole monomer.
(2)
In
n is an integer of 16 to 19;
In a preferred embodiment, the polymer may have a number average molecular weight (Mn) of 7500-8300.
In a preferred embodiment, the polymer may have a weight average molecular weight (Mw) of 7800-8500.
In another embodiment of the present invention, there is provided a process for preparing a polyol, which comprises the steps of: a) dissolving the novel pyrrole monomer in a solvent together with trans-1,2-Bis (tri-n-butylstannyl) ethylene, followed by stirring and reacting;
b) adding a solvent in the presence of a palladium catalyst, and then stirring the mixture while applying an electromagnetic wave;
c) adding 2- (tributylstannyl) thiophene to the mixture, and stirring the mixture while applying an electromagnetic wave, thereby producing a polymer synthesized from the synthesized pyrrole monomer represented by the following formula (2a).
≪ EMI ID =
In Formula (2a), R 1 is
In one embodiment, the palladium catalyst may be a catalyst in which Tetrakis (triphenylphosphine) palladium (0) and tri (o-tolyl) phosphine are mixed or Tetrakis (triphenylphosphine) palladium (0).
In a preferred embodiment, the polymer may have a number average molecular weight (Mn) of 7500-8300.
In a preferred embodiment, the polymer may have a weight average molecular weight (Mw) of 7800-8500.
In another embodiment, the present invention is achieved by providing a compound synthesized from a pyrrole monomer represented by the following formula (3) synthesized using the novel pyrrole monomer.
(3)
In
≪ Formula 3-1 >
A =
(3-2)
A =
<Formula 3-3>
A =
In another embodiment of the present invention, the novel pyrrole monomer is selected from the group consisting of tributyl (thiophen-2-yl) stannane, tributyl (phenyl) stannane, tributyl (2,3-dihydrothieno [ -7-yl) stannane with a solvent in the presence of a palladium catalyst, and then refluxing with heating while stirring to prepare a compound synthesized from the pyrrole monomer represented by the following formula (3a) ≪ / RTI >
≪ EMI ID =
In the general formula 3a, A is one selected from the group consisting of formulas 3a-1, 3a-2, 3a-3 are defined below, R 1 is an alkyl of C4 ~ C17, R 2 is alkyl of C1 ~ C6 .
≪ General Formula (3a-l)
A =
≪ General Formula (3a-2)
A =
≪ General Formula (3a-3)
A =
In a preferred embodiment, the palladium catalyst may be a catalyst in which Tetrakis (triphenylphosphine) palladium (0) and tri (o-tolyl) phosphine are mixed or Tetrakis (triphenylphosphine) palladium (0).
The novel pyrrole monomers of the present invention having the above-described characteristics can be obtained by introducing an alkyl chain into the polypyrrole derivatives, which are insoluble in organic solvents, to have high solubility, And can also form compounds with various molecules.
Specifically, the novel pyrrole monomer according to the present invention has a structure in which polymer polymerization through an electrochemical reaction is very easy and can be utilized as a monomer capable of easily synthesizing a new polymer through a circulating current method, Can be very useful as a novel monomer capable of forming a copolymer with other monomers. Monomers having such a skeleton have very good physical properties for the production of solar cells at present.
The novel copolymers synthesized from the pyrrole monomers according to the invention also have low steric hindrance, low bandgaps and high conductivity. In particular, a polymer using a novel pyrrole monomer has a wide absorption range from 400 nm to 900 nm through a UV-vis spectrum and can be applied to a solar cell with a maximum absorption at a wavelength of 650 nm, and a bandgap calculated from a cyclovoltammogram data Has a low band gap of 1.28 eV, which can be applied to solar cells, OLED, and the like.
The compounds synthesized from the pyrrole monomers according to the present invention not only have excellent electronic properties but also have high solubility in both polar and nonpolar organic solvents and thus can be applied to solar cells or LED devices, It has an advantage that it can be applied. That is, the compound according to the present invention exhibits a considerable bathochromic shift compared to a monomer as a precursor and emits blue-based light, thus confirming the applicability of the compound as an active layer of an LED device. It is also possible to apply the synthesized polymer as a monomer to the LED industry.
The novel monomers, polymers and compounds according to the present invention as described above are useful inventions having various effects and are highly expected to be used in industry.
Figure 1 is the formula of the novel pyrrole monomer according to the invention,
2 is a process diagram showing a process for synthesizing a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 3A is a graph showing 1 H-NMR characteristics of a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 3B is a graph showing 13 C-NMR characteristics of a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 3c is a graph showing ultraviolet-visible (UV-vis) absorption spectroscopic characteristics of a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 3D is a graph showing infrared (IR) absorption spectroscopic characteristics of a novel pyrrole monomer according to an embodiment of the present invention,
4 is a schematic diagram showing a process for synthesizing a polymer using a novel pyrrole monomer according to an embodiment of the present invention (Poly (2-heptadecyl-5-hexyl-4-vinylpyrrolo [3,4-d] thiazole)
5A is a graph showing 1 H-NMR characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 5B is a graph showing infrared (IR) absorption spectroscopic characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 5c is a graph showing ultraviolet-visible (UV-vis) absorption spectroscopic characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 5D is a graph showing the characteristics of a thermogravimetric analyzer (TGA) of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention,
FIG. 5E is a graph showing a cyclic voltammogram characteristic of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention,
Figure 6 is a schematic diagram of the preparation of the compound (2-heptadecyl-5-hexyl-4,6-di (thiophen-2-yl) -5H-pyrrolo [3,4- d] thiazole ), Which is a reaction scheme,
FIG. 7A is a graph showing 1 H-NMR characteristics of the compound synthesized according to FIG. 6,
FIG. 7B is a graph showing 13 C-NMR characteristics of the compound synthesized according to FIG. 6,
FIG. 7C is a graph showing the ultraviolet / luminescence absorption spectroscopic characteristics of the compound synthesized according to FIG. 6,
FIG. 7D is a graph showing infrared absorption spectroscopic characteristics of the compound synthesized according to FIG. 6,
8 is a graph showing the results of the synthesis of 2-heptadecyl-5-hexyl-4,6-diphenyl-5H-pyrrolo [3,4-d] thiazole according to another embodiment using the novel pyrrole monomer of the present invention. ego,
FIG. 9A is a graph showing the 1 H-NMR characteristics of the compound synthesized according to FIG. 8,
FIG. 9B is a graph showing 13 C-NMR characteristics of the compound synthesized according to FIG. 8,
FIG. 9c is a graph showing the ultraviolet / luminescence absorption spectroscopic characteristics of the compound synthesized according to FIG. 8,
FIG. 9D is a graph showing infrared (IR) absorption spectroscopic characteristics of the compound synthesized according to FIG. 8,
FIG. 10 is a graph showing the effect of the compound (2-heptadecyl-5-hexyl-4,6-bis (2,3-dihydrothieno [3,4- b] [1,4] dioxin-7-yl) -5H-pyrrolo [3,4-d] thiazole)
FIG. 11A is a graph showing the 1 H-NMR characteristics of the compound synthesized according to FIG. 10,
FIG. 11B is a graph showing 13 C-NMR characteristics of the compound synthesized according to FIG. 10,
FIG. 11C is a graph showing the ultraviolet / luminescence absorption spectroscopic characteristics of the compound synthesized according to FIG. 10,
11 (d) is a graph showing infrared (IR) absorption spectroscopic characteristics of the compound synthesized according to FIG.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a pyrrole monomer having a structure represented by the following general formula (1) wherein a thiazole group is introduced into a novel pyrrole monomer of the present invention and Br is substituted with a halogen element.
≪
In the formula of the novel pyrrole monomer R 1 is an alkyl of C4 ~ C17, R 2 is alkyl of C1 ~ C6.
2 is a process diagram showing a process for synthesizing a novel pyrrole monomer (4,6-dibromo-2-heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole) according to an embodiment of the present invention. Heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole which is a pyrrole monomer according to an embodiment having the structure of
As a preliminary step for synthesizing the pyrrole monomer of the present invention, 4,6-dibromo-2-heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole, 2-heptadecyl-thiazole).
3.18 g (6.3 mmol) of the above compound 1 (4,5-bis-bromomethyl-2-heptadecyl-thiazole) was dissolved in 80 ml of benzene, and the solution was cooled at 6 to 10 ° C. and the freezing point of benzene was 5.5 ° C. ) Under a water bath, a solution of 1.9 g (18.8 mmol) of hexylamine in 80 ml of benzene was slowly added dropwise and stirred for 1 hour in a cold water bath (6-10 ° C, freezing point of benzene was 5.5 ° C or lower) Stir at room temperature for 48 hours. The resulting hexylammonium bromide is removed by filtration, and the filtered organic layer is stirred for 48 hours. Then hexylammonium bromide is removed by filtration and stirred for 24 hours. 2-heptadecyl-5-hexyl-5 (2-heptadecyl-5-hexyl-5) was synthesized in the form of a white solid with a silica gel column (methylene chloride: hexane = 1: 1) , 6-dihydro- 4H -pyrrolo [3,4-d] thiazole) (33% yield).
On the other hand, the additive disclosed in the above embodiment is sufficient if it is an amine having an alkyl group (C1-C6).
The solvent can be an organic solvent such as toluene as well as benzene.
In addition, 3 equivalents of hexylamine having an alkyl group attached thereto was added in the above-mentioned example. This is because the equivalent of 3 equivalents is the minimum equivalent amount required for the reaction. Since there is a problem of side reaction, it is preferable to add up to 3.5 equivalents.
0.93 g (2.1 mmol) of compound 2 (2-heptadecyl-5-hexyl-4,5,6,6a-tetrahydro-pyrrolo [3,4-d] thiazole) synthesized in the above step was dissolved in 350 ml of dry toluene After that, a solution of 0.52 g (2.28 mmol) of 1,2-dichloro-5,6-dicyano-hydroquinone in 150 ml of toluene is slowly added dropwise at -40 ° C. Thereafter, the temperature is gradually raised, and the mixture is stirred at 0 to 5 ° C for 3 hours. The solution was distilled at 40 ° C or lower and 0.92 g (99%) of compound 3 (2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole) synthesized by silica column (methylene chloride) was obtained.
As a preferable reaction, the use of 1,2-dichloro-5,6-dicyano-hydroquinone (DDQ) and toluene as shown in the above-mentioned Example shows a high yield after the reaction, -dichloro-5,6-dicyano-hydroquinone) may be used.
In the above, when 1 to 1.1 equivalents of DDQ is added, sufficient reaction occurs.
After dissolving 0.92 g (2.05 mmol) of synthesized compound 3 (2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole) in 50 ml of methylene chloride, 0.7 g (8.3 mmol) of sodium bicarbonate is added dropwise. Then add 0.2 ml of bromine in 10 ml of methylene chloride at 0 ° C slowly dropwise. The resulting solid is filtered and filtered, and DI water is added to terminate the reaction, and the organic layer is extracted. The extracted organic layer was distilled and passed through a silica gel column (methylene chloride: hexane 1: 4) to obtain the compound 4 (4,6-dibromo-2-heptadecyl-5- hexyl-5H-pyrrolo [3,4-d] thiazole (1.06 g, 86%).
In addition to the above bromine, NBS (N-bromosuccinimide) may be used. When using NBS, sodium bicarbonate is not necessary and NBS can be dissolved in MC (methylene chloride) and added 2 ~ 2.1 equivalents.
Since the bromine is attached to both sides, 2 equivalents are used for the reaction, so 2 ~ 2.05 equivalents are added. No more is added since side reactions may occur.
In addition, sodium bicarbonate is added in an excess amount. In the above examples, 4 equivalents are added, but up to 8 equivalents may be added.
The physical properties of the synthesized
In FIG. 3A, it can be seen that in the NMR data of the previous material, the 1H site peak was brominated by disappearance of Br substitution.
Also in FIG. 3D, it can be seen that the sp 3 CH peaks on the right side of 3000 have many alkyl chains.
FIG. 4 is a schematic diagram showing a process for synthesizing a polymer (2-heptadecyl-5-hexyl-4-vinylpyrrolo [3,4-d] thiazole) using a novel pyrrole monomer according to an embodiment of the present invention.
(2)
Wherein R 1 is
The polymer has a number average molecular weight (Mn) of 7500 to 8300 and a weight average molecular weight (Mw) of 7800 to 8500.
The thiophene at the terminal is an end capped polymer. When end capping is performed, no polymerization occurs at the end.
Will be described below for the synthesis of the Formula (2) the present invention the polymer Poly (2-heptadecyl-5- hexyl -6-vinyl-5 H -pyrrolo [3,4-d] thiazole) (PHHVPT) of having the structure.
Then, a small amount of toluene, in which the catalyst tris (dibenzylideneacetone) dipalladium (0) and tri (o-tolyl) phosphine are dissolved in a 1: 4 equivalent ratio, is added and stirred at the same temperature for 1 hour while applying 50 W of electromagnetic wave.
After that, 2- (tributylstannyl) thiophene was added to 10 mol% (0.1 equivalent) of
Tetrakis (triphenylphosphine) palladium (0) may be used instead of the catalyst provided in the above reaction, or chlorobenzene may be used as a solvent.
It is preferable that the
Also, it is preferable to add the equivalence ratio of tris (dibenzylideneacetone) dipalladium (0) and tri (o-tolyl) phosphine in an equivalent ratio of 1 to 4, Even when the ratio is 2 to 8 equivalents, the synthesis of the polymer according to the present invention occurs.
The synthesis of the invention polymers Poly - water sexual characteristics of (2-heptadecyl-5-hexyl -6-vinyl-5 H pyrrolo [3,4-d] thiazole) (PHHVPT) is shown in Figures 5a to 5e.
FIG. 5A is a graph showing 1 H-NMR (10000 times) characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention, and FIG. FIG. 5C is a graph showing ultraviolet-visible (UV) absorption spectroscopic characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention FIG. 5D is a graph showing a TGA characteristic of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention, FIG. 5E is a graph showing the TGA characteristics of a polymer synthesized from a novel pyrrole monomer according to an embodiment of the present invention (Cyclovoltammogram) characteristic of the present invention.
FIGS. 5A and 5B are data for analyzing the existence and structure of functional groups of the polymer. Referring to FIG. 5A, the monomer and the polymer having a double bond are observed in a similar pattern to 1H-NMR data of the monomer, As shown in Fig.
In addition, it can be seen there is a double bond when viewed by looking at the Fig. 5b has a number of alkyl chain bore 3000 into the right side of the sp 3 CH peak is 3000 as the left side of the sp 2 CH peak Hou.
In FIG. 5c, it is seen that the polymer is produced because it is red-shifted from the UV-vis spectrum of the monomer and absorbs a wider range. It can be seen that the polymer can be applied to the solar cell because it shows that the polymer shows a wide absorption range from 400 nm to 900 nm through the UV-vis spectrum shown and shows the maximum absorption at a wavelength of 650 nm.
In FIG. 5d, the thermal stability is known through the TGA data. It is gradually decomposed at about 210 ° C., and the weight is reduced by about 23% while the temperature reaches 363 ° C., while the weight is decreased by 43.2% Respectively. The reason for this is that the decomposition starts at about 200 ° C and is rapidly decomposed at 300 ° C because the temperature at which the alkyl group of the unit contained in the polymer breaks. Particularly, the weak ethylene group is introduced in the heat, resulting in two sudden weight reduction curves.
Figure 5e also shows the onset oxidation potential at a voltage of 0.47 eV in the cyclovoltammogram data and the onset reduction potential at -0.81 eV. The band gap calculated by this difference shows a low band gap of 1.28 eV. From this, it can be seen that it can be applied to solar cells, OLED, and the like.
Hereinafter, the
The compound according to the present invention has the following general formula (3).
(3)
The R 1 Is a (C4 ~ C17), and, R 2 is (C1 ~ C6) alkyl,
A at both ends is a group substituted with one selected from the group consisting of the structural formulas (3a), (3b) and (3c) defined below at the time of synthesis when Br at both ends of the formula (1)
≪ EMI ID =
A =
≪ EMI ID =
A =
≪ Formula 3c >
A =
FIG. 6 is a graph showing the synthesis of a compound (2-heptadecyl-5-hexyl-4,6-di (thiophen-2-yl) -5H-pyrrolo [3,4-d] thiazole) using the novel pyrrole monomer of the present invention As shown in the reaction scheme, the synthesized compound has a structure represented by the following formula (4).
≪
The R 1 Is (C4 to C17), and R < 2 > is (C1 to C6) alkyl.
Preparation of
5mL of toluene in 100mL flask,
The temperature of the reaction mixture is then lowered to room temperature and stirred for 1 hour. To the reaction mixture was added Hexane And 50 mL of H 2 O are added thereto, and then the organic layer is separated. The obtained organic layer was dried over MgSO 4 to remove moisture, and then the solvent was distilled off under reduced pressure. The obtained organic mixture was then subjected to column chromatography (eluent: dichloromethane / Hexane = 3/10, vol / vol) to separate the compound 5 (yield: about 52%).
On the other hand, chlorobenzene may be used as the solvent, and tris (dibenzylideneacetone) dipalladium (0) and tri (o-tolyl) phosphine may be used as a catalyst in a one to four equivalent ratio.
The tributyl (thiophen-2-yl) stannane reacts with two equivalents of the stannane to form a compound.
In the case of the catalyst, 0.04 equivalent is added to the reaction.
The physical properties of the synthesized
FIG. 7A is a graph showing 1 H-NMR characteristics of the compound synthesized according to FIG. 6, FIG. 7B is a graph showing 13 C-NMR characteristics of the compound synthesized according to FIG. 6, FIG. 7D is a graph showing infrared (IR) absorption spectroscopic characteristics of the compound synthesized according to FIG. 6. FIG.
7A, 7B and 7D are NMR and IR data for the presence or absence of the functional group of the compound and the structural analysis.
Referring to FIG. 7a, a total peak of 5H between 7 and 8 ppm is observed in the portion similar to the NMR data of the monomer, which indicates that the monomer and thiophene are compounds.
7c, it can be seen that the compound is synthesized through red shift of the monomer. In the graph of FIG. 7c, the compound exhibits a considerable bathochromic shift compared with the monomer as the precursor and emits blue light Able to know. The polymer can be easily polymerized through the cyclic current method because it has a very easy structure to polymerize through electrochemical reaction. Also, it is known that substitution of bromide as a functional group at the terminal can be very useful as a new monomer capable of forming a copolymer with other monomers, and monomers having such a skeleton are very effective in current solar cells. In addition, since it shows blue light emission, it is confirmed that it can be applied to the active layer of LED device, and it is possible to synthesize synthesized compound or similar derivative and synthesized polymer as a monomer, It is possible.
Also, FIG. 7d shows that the sp 3 CH peaks on the right side of 3000 have many alkyl chains and the sp 2 CH peaks on the left side of 3000 indicate double bonds.
FIG. 8 is a graph showing the effect of the compound (2-heptadecyl-5-hexyl-4,6-diphenyl-5H-pyrrolo [3,4-d ] thiazole), and the synthesized compound has a structure represented by the following formula (5).
≪
Preparation of
To a 100 mL flask was added 3 mL of toluene, 0.1 g of 4,6-dibromo-2-heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole as
The solvent may be chlorobenzene, and tris (dibenzyl ideneacetone) dipalladium (0) and tri (o-tolyl) phosphine may be used in a one to four equivalent ratio as the catalyst.
Since the tributyl (phenyl) stannane forms a compound by reacting with 2 equivalents, 2 equivalents of the tributyl (phenyl) stannane are added to a sufficient amount of 2.6 equivalents. In the case of the catalyst, 0.04 equivalent is added to the reaction.
The physical properties of the synthesized
FIG. 9A is a graph showing 1 H-NMR characteristics of the compound synthesized according to FIG. 8, FIG. 9B is a graph showing 13 C-NMR characteristics of a compound synthesized according to FIG. 8, FIG. 9D is a graph showing infrared (IR) absorption spectroscopic characteristics of a compound synthesized according to FIG. 8. FIG.
9A, 9B and 9D are NMR and IR data for the presence or absence of the functional group of the compound and the structural analysis.
Referring to FIG. 9a, a total peak of 10H between 7 and 8 ppm is observed in the portion similar to the NMR data of the monomer, which indicates that the monomer and the benzene ring are compounds.
In FIG. 9c, it can be seen that the compound is synthesized through red shift of the monomer. In the graph of FIG. 9c, the compound shows a bathochromic shift compared to the monomer as the precursor and emits blue light . The polymer can be easily polymerized through the cyclic current method because it has a very easy structure to polymerize through electrochemical reaction. Also, it is known that substitution of bromide as a functional group at the terminal can be very useful as a new monomer capable of forming a copolymer with other monomers, and monomers having such a skeleton are very effective in current solar cells. In addition, since it shows blue light emission, it can be applied to an active layer of an LED device, and it can be applied to a LED industry by synthesizing a synthesized compound or a derivative containing such a compound and a synthesized polymer as a monomer .
Also, FIG. 9d shows that the sp 3 CH peaks on the right side of FIG. 3 have many alkyl chains, and the sp 2 CH peaks on the left side of FIG. 3 indicate double bonds.
10 is a graph showing the effect of the compound (2-heptadecyl-5-hexyl-4,6-bis (2,3-dihydrothieno [3,4- b] [1,4] dioxin-7-yl) -5H-pyrrolo [3,4-d] thiazole).
(6)
Preparation of
To a 100 mL flask was added 5 mL of toluene, 0.1 g of 4,6-dibromo-2-heptadecyl-5-hexyl-5H-pyrrolo [3,4- d] thiazole, tributyl (2,3-dihydrothieno [ b] [1,4] dioxin-7-yl) stannane and 0.0096 g of tetrakistriphenyl phosphine paladium, Pd (PPh 3 ) 4 . Then, the reaction mixture was stirred at room temperature until the reaction mixture was dissolved in a transparent solution, and the temperature was gradually raised to 110 DEG C and stirred while being refluxed for 48 hours. The temperature of the reaction mixture is then lowered to room temperature and stirred for 1 hour. The obtained organic mixture was subjected to column chromatography (eluent: dichloromethane / hexane = 1/2, vol / vol) to separate Compound 7 (yield: about 54%).
Chlorobenzene may be used instead of the solvent, and tris (dibenzylideneacetone) dipalladium (0) and tri (o-tolyl) phosphine may be used in a ratio of 1 to 4 equivalents.
The tributyl (2,3-dihydrothieno [3,4-b] [1,4] dioxin-7-yl) stannane reacts with two equivalents to form a compound.
In the case of the catalyst, 0.04 equivalent is added to the reaction.
The physical properties of the synthesized
FIG. 11A is a graph showing the 1 H-NMR characteristics of the compound synthesized according to FIG. 10, FIG. 11B is a graph showing 13 C-NMR characteristics of the compound synthesized according to FIG. 10, FIG. 11D is a graph showing infrared (IR) absorption spectroscopic characteristics of a compound synthesized according to FIG. 10; FIG.
11A, 11B and 11D are NMR and IR data for the presence or absence of the functional group of the compound and the structural analysis.
Referring to FIG. 11A, 2H and 4H-side 8H peaks between 6 and 7 ppm are observed in the portion similar to the NMR data of the monomers, indicating that monomers and EDOT are compounds.
In FIG. 11C, it can be seen that the compound is synthesized through red shift. In the graph of FIG. 11C, the compound shows a bathochromic shift compared to the monomer as the precursor and emits blue light. . The polymer can be easily polymerized through the cyclic current method because it has a very easy structure to polymerize through electrochemical reaction. Also, it is known that substitution of bromide as a functional group at the terminal can be very useful as a new monomer capable of forming a copolymer with other monomers, and monomers having such a skeleton are very effective in current solar cells. In addition, since it shows blue light emission, it can be applied to an active layer of an LED device, and it can be applied to a LED industry by synthesizing a synthesized compound or a derivative containing such a compound and a synthesized polymer as a monomer .
11d, it can be seen that the sp 3 CH peaks on the right side of 3000 have many alkyl chains and the sp 2 CH peaks on the left side of 3000 indicate double bonds.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents. Of course, such modifications are within the scope of the claims.
(1): 4,5-bis-bromomethyl-2-heptadecyl-thiazole
(2): 2-heptadecyl-5-hexyl-5,6-dihydro-4H-pyrrolo [3,4- d] thiazole
(3): 2-heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole
(4): 4,6-dibromo-2-heptadecyl-5-hexyl-5H-pyrrolo [3,4-d] thiazole
(5): 2-heptadecyl-5-hexyl-4,6-di (thiophen-2-yl) -5H pyrrolo
[3,4-d] thiazole
(6): 2-heptadecyl-5-hexyl-4,6-diphenyl-5H-pyrrolo [3,4- d] thiazole
(7): 2-heptadecyl-5-hexyl-4,6-bis (2,3-dihydrothieno [3,4-b] [1,4] dioxin- d] thiazole
Claims (13)
[Chemical Formula 1]
Wherein R 1 is C 4 to C 17 alkyl and R 2 is C 1 to C 6 alkyl.
b) Addition of 1,2-dichloro-5,6-dicyano-hydroquinone to the synthesized 2-heptadecyl-5-hexyl-5,6-dihydro- 4H- pyrrolo [3,4-d] To synthesize 2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole;
c) Preparation of a novel pyrrole monomer represented by the following formula (1a) synthesized by dissolving synthesized 2-heptadecyl-5-hexyl-pyrrolo [3,4-d] thiazole in a solvent and then adding bromine or N-bromosuccinimide :
[Formula 1a]
In Formula (1a), R 1 is C 4 to C 17 alkyl and R 2 is C 1 to C 6 alkyl.
Wherein the alkyl group on the amine in step a) comprises C1 to C6 alkyl.
(2)
In Formula 2, R 1 is C 4 to C 17 alkyl, R 2 is C 1 to C 6 alkyl,
n is an integer of 16 to 19;
Wherein the polymer has a number average molecular weight (Mn) of 7500-8300.
Wherein the polymer has a weight average molecular weight (Mw) of 7800-8500.
b) adding a solvent in the presence of a palladium catalyst, and then stirring the mixture while applying an electromagnetic wave;
c) adding 2- (tributylstannyl) thiophene to the mixture, and stirring the mixture while applying an electromagnetic wave, wherein the polymer is synthesized from the pyrrole monomer represented by the following formula
≪ EMI ID =
In Formula (2a), R 1 is C 4 to C 17 alkyl, R 2 is C 1 to C 6 alkyl,
n is an integer having a value between 16 and 19;
Wherein the palladium catalyst is a catalyst in which Tetrakis (triphenylphosphine) palladium (0) and tri (o-tolyl) phosphine are mixed or Tetrakis (triphenylphosphine) palladium (0).
Wherein the polymer has a number average molecular weight (Mn) of 7500-8300.
Wherein the polymer has a weight average molecular weight (Mw) of 7800-8500.
(3)
In Formula 3, A is a group selected from the group consisting of Formulas 3-1, 3-2 and 3-3 defined below, R 1 is C4-C17 alkyl, and R 2 is C1-C6 alkyl .
≪ Formula 3-1 >
A =
(3-2)
A =
<Formula 3-3>
A =
≪ EMI ID =
In the general formula 3a, A is one selected from the group consisting of formulas 3a-1, 3a-2, 3a-3 are defined below, R 1 is an alkyl of C4 ~ C17, R 2 is alkyl of C1 ~ C6 .
≪ General Formula (3a-l)
A =
≪ General Formula (3a-2)
A =
≪ General Formula (3a-3)
A =
Wherein the palladium catalyst is a catalyst in which Tetrakis (triphenylphosphine) palladium (0) and tri (o-tolyl) phosphine are mixed or Tetrakis (triphenylphosphine) palladium (0).
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